Production of industrial gases containing carbon monoxide and hydrogen



A g- 9, 1952 E. s. CORNER ET-AL 2,607,658

I PRODUCTION OF INDUSTRIAL GASES CONTAINING CARBON MONOXIDE AND HYDROGEN Original Filed Aug. 12, 1947 Patented Aug. 19, 1952 PRODUCTION OF INDUSTRIAL GASES CON- TAINING CARBON MONOXIDE AND HY- DROGEN Eugene S. Corner, Roselle, Robert V. J. McGee,

Union, and Charles S. Lynch, Plainfield, N. J assignors to Standard Oil Development Company, a corporation of Delaware Original application August 12, 1947, Serial No.

768,248. Divided and this application February 4, 1948, Serial No. 6,226

11 Claims.

This application is a division of our copending application Ser. No. 768,248 filed August 12, 1947, now U. S. Patent No. 2,507,502 dated May 16, 1950.

The present invention is directed to a method forproducing industrial gases containing carbon monoxide and hydrogen from gaseous hydrocarbons and to novel compositions useful as oxygen carriers in the oxidation of gaseous hydrocarbons.

In many industrial processes the raw material is composed of, or essentially contains, a mixture of carbon monoxide andhydrogen. Chief among these processes are the so-called methanol synthesis, in which carbon monoxide and hydrogen are reacted in the presence of a suitable catalyst to produce oxygenated organic compounds, and the Fischer-Tropsch synthesis, in which carbon monoxide and hydrogen in suitable proportions are reacted in the presence oi.

a suitable catalyst and under selected conditions to. produce a product primarily composed of liquid hydrocarbons. In processes of this typeit is highly desirable that the feed gas be free from contamination with inert gaseous substances.

The obvious way to obtain a mixture of carbon monoxide and hydrogen is to subject a mixture of a hydrocarbon such as methane and air to controlled combustion. This procedure, however, results in a gas containing a large quantity of nitrogen. This detrimental dilution has led to much study and experimentation, directedtoward the development of a method for producing the desired "make gas free from contaminants and diluents.

Among the procedures which have been proposed for producing from hydrocarbons a suitable gas mixture containing carbon monoxide and hydrogen free from large volumes of diluent gas is that in which a metal is used as an oxygen carrier. The general procedure proposed is to react the hydrocarbon, such as methane, with a metal oxide until the latter is depleted in oxygen content, then to reoxidizethe depleted metal carrier with air, venting olf the residue gases, and again reacting the regeneratedoxide with the hydrocarbon. By this procedure the gas resulting fromthe reaction of the hydrocarbon with the metal oxide is obtained separate.- ly from the gaseous residues from the oxidation of the metal with air.

While a number of metals have been proposed for use in this process they all present difierent problems when it is attempted actually to use them in the process. Zinc oxide is one which theoretically should serve the purpose admirably because its oxidation potential is such that it is practically impossible to oxidize a hydrocarbon with zinc oxide to carbon dioxide whereby a high selectivity to carbon monoxide can be expected in the use of this metal oxide. Zinc oxide, however, presents the great difiiculty that at the temperature at which it will give up its oxygen the zinc Will also vaporize, giving rise to a diflicult recovery problem. Moreover, zinc oxide does not effect a sufficiently high conversion of the hydrocarbon.

Of the many oxides which might be considered useful, iron oxide, based on the considerations of set the iron oxide oxidizes the hydrocarbon completely to carbon dioxide until an appreciable quantity of free iron is present in the reaction mass. From that point on some carbon monoxide is produced but at the same time large quantities of carbon are produced by reason of the highly catalytic efiect of the iron on the cracking of hydrocarbons.

Among the metal oxides which have been suegested as an alternative for iron is titania. This oxide shows considerable promise as an oxygen carrier, particularly when using the technique known as the fluidized solids technique inwhich the carrier in finely divided form is suspended in a rising stream of the hydrocarbon gas to be oxidized in such a manner as to form a dense,

fluidize d suspension in which the solid particles metal oxides, which are solid and reducible at a temperature between 1600 and 2400 F., of which vention'are iron, manganese, chromium, nickiel,.

cobalt and tungsten. Mixtures .ofdthese oxides are particularly suitable.

A prefer-red carrier according to the present invention is titania associated with the oxides of iron, nickel and chromium. 'Inthis composition the titania should constitute at leastabout The remainder of the'cornposi tion may be made up of the'other three' oxides Suitable proportions forv the other three components are 80 'FezOs, 10

The pro- 90% by weight.

in variable proportions.

nickel oxide and 10 chromium oxide. portions of nickel oxide and chromium oxide in this mixture can be increased considerably at the expense of the iron oxide.

' A composition of this type may be-made in various ways. The various oxides can bemixed mechanically into a homogeneous mixture.

'More intimate mixing may be realizedby copre 'cipitation of the various oxides from mixed solutions of their salts; Again, one of the oxides may :be impregnated with "a solution of 7 a salt ofthe other oxide". or other oxides and the impregnated oxide dried and calcined. {Of the various methods of'lmix'ing the; coprecipitation ispreferred. 1 f Y In preparing mixed oxygen Carriers according "to the present invention-consideration must be given to the fluidizability of theresulting product. -When iron oxide alone is used with titania in the form of a mechanical mixture it, should not be present in amounts such aStodnterfere with the fiuidization of the finely divided mixture. Iron oxide has a tendencyto' become sticky at the operating temperature specified and ifit isemployed in substantial amounts it tends to cause agglomeration which renders fluidization difficult. Accordingly, in this instance the iron'oxide should not constitutemore than about 4% by weight of the total mixture.

vChromium oxide, on the other-hand, can be 'tolerated in'much larger amounts. Mixtures of titania and chromium oxide containing up to 50% by'weight of the latter arecontemplated for use in accordance with the present invention.

'Manganese oxide and tungsten oxide may also i be tolerated in amounts comparable to those specified for chromium oxide. 'Nickel and cobalt oxides, on the other-hand, should be used more sparingly, it being'preferred to keep'their content'when they are employed with titania below about by weight; Itwill be understood that the limits given for the oxides of iron, nickel and cobalt may -'be iincreased 'when an oxide, such as chromium oxide, is used conjointly with them.

fI'heseilimits on the contents of the various addition agents are given primarily in the interest of the fiuidizability ofthe resultingoxygen carrier. Hereinafter when .mixtures. -.of .these various, .oxides are referred to as fluidizable, it is intended toindicate that they are-present in the .mixture within the limits specified above. Itis to be borne in .mind, however, that the use of these oxygen carriers is-notconfinedrto the 4 fluidized solid technique since they may also be used in fixed bed operations.

In the practice of the present invention according to the fluidized solid technique, the solid oxygen carrier is employed in the form of fine particles none of which is substantially larger than 10 mesh and the bulk of which is smaller .than about, 100=mesh.. -Eor good fiuidization it is preferredthat" .the powdered material include particles of various sizes ranging upwardly from .about 5 micron and containing a substantial tract on. between about 2 00 and 400 mesh. With .solidsrin theirforegoing particle size range, suitablefluidization is realized by flowing the gas upwardly through the finely divided solids at a velocity ranging from about .3 to 5 ft./second. It :will -be understood that lower gas velocities maybe-employed in which case the action may be "more properly described as jiggling than fluidization. ,Any type of mixing in which there is .wmovem'ent ofthe solid particles in the gas in such away as tomaintain a, substantially homogeneiupper'end located at the intended level of the :dense' phase of thesuspensio-n in vessel 2. Duct ous composition of solids throughout the reaction zone in the form of adense suspension containing upwards of 5% by volume of solids is satis- "factory for the-practice of the presentinvention.

The-temperature maintained in the contacting zone in which the hydrocarbon is converted should be at least about 1600 F. and will-usually be'between 1600 F. andabout 2000 F. There is no actual upper-limit on this-temperature except that dictated by the melting point of'the finely divided solid in the contacting zone or the melting point of the material-of hichth-cbntacting vessel is made.

The nature of'the present invention may be more clearly understood-from the following detailed description of the accompanying drawing in which the single figure is a front elevation in diagrammatic form of one type of apparatus =suitable=forthe practice of the present invention.

Referring to the drawing in detail numeral 4 designates. a reaction-vessel-and numeral 2 designatesa regeneration vessel. In the'e'rnbodiment shown these vessels'operate on the=dense phase drawoifprinciple. It Will 'be understood that these vessels can be oi the well known bottom drawoif type or the strictly upil w'type.

Vessel l is provided'atits'bottom with an inlet 2 for gas and finely divided solid and at its upper end with an outlet 3 for gas ahead of -which is'an internal cyclone 3 or other separator 'for gases and solid-shaving a-dip leg Sdepending into .thevessel. On one wall the vessel is provided with a duct 6 having its open upper end terminating at the selected level for the dense phase of the suspension. "This duct empties into a line? into which air or other oxidizing gas is fed through line 8. Line '7 discharges into the bottom of vessel 2 which, like vessel I, is provided at its upper end'with a gas vent 9 ahead of which "isarrangeda cyclone separator 10 having a dip "leg-i1 extending into" the dense phase of the suspension in vessel'Z. VesselZ is also provided with a duct "[2011 one of its walls having its open IZ'empties into line Zinto which is fed a hydrocarbon gas through line 13.

I In carrying out the'process-of the present in- 'vention llTthe apparatus described, the vessels are charged with finelydividedsolid the indi- --vidual particles of which are composed of titania impregnated or mixedwith iron oxide and/or one or more of the other addition agents specifled. As previously indicated, thismixture is [conveniently prepared by mixing aqueous solutions of a titanium salt and an iron salt and copreeipitating the hydroxides with an alkali. The precipitate is carefully washed to remove watersoluble contaminants after which it is dried and roasted. If the final product is not in the finely divided form heretofore specified, it is ground so as to satisfy the requirements.

In starting up with both vessels charged with the finely divided solid mentioned above, the system may be brought to a temperature between about 1550 and 1850 F. by feeding hot combustion gases through lines 8 and [3. If desired,

some .finely divided carbon may be mixed with the initial charge and the system brought to temperature by burning off the carbon. When the operating temperature is attained, a hydrocarbon gas is fed through line I3 at a velocity such as to maintain the finely divided solid in vessel l in susp nsion in the gas in the form of a dense body in which the particles are in incessant motion. The velocity should be so regulated as to produce a suspension having at least about 5% by volume of solids, preferably between about and 25%. The velocity is correlated with the amount of solids charged so as to bring the level of the dense phase to a point where it overflows into conduit 6. The gases passing out of the vessel tend to carry solids with them. These solids are separated in the cyclone 4 and returned to the dense suspension.

As the solid overflows into conduit 6 and thus into 'line 1, preheated air or other oxidizing medium is fed in through line 8 at a velocity such as to carry the finely divided solid into vessel '2 and maintain it therein in a suspension of the character heretofore described, the level of the dense phaseof the suspension being so regulated that the dense phase overflows into conduit l2 which carries solid back into line 2'.

The heat required for the reaction in vessel 1 is supplied primarily as sensible heat contained in the solids returned from vessel 2 supplemented by preheat imparted to the hydrocarbon gas from the hot exhaust gas from vessel 2.

It will be appreciated that the illustration of the apparatus and the drawing is limited to the bare essentials, calculated merely to depict the flow plan of the process. Design and engineering details are purposely omitted to avoid unnecessary complication. Among such details are 'heat'exchangers, aerating jets for the various conduits, pumps, and the like. It is repeated that the flow plan shown is only one of several which may be used, the essential requirement being that the flow plan shall include at least two zones in one of which hydrocarbon is reacted with the metal oxide mixture serving asthe oxygen carrier and in the other of which the resultant metal or metal-metal oxide mixture with depleted oxygen content is treated with an oxidizing gas so as to replenish its oxygen content.

In order to illustrate the improved results obtainable by the practice of the present invention, the following examples of actual operations are presented:

EXALEPLE I Methane was converted by contact with titania alone and titania mixed with different amounts of iron oxide in separate operations utilizing the fluidized solid technique. In these operations the oxygen carrier was employed in finely divided form having a wide range of particle size, in-

cluding particles as small as 5 microns and a substantial proportion of particles between 200 and.

400 mesh with all of theparticles passing 3100 mesh. The operating conditions and resultsare given in the following table: I

Effect of added, iron omide to TiOz on methane conversion and selectivity to CO [Fluid bed; 200 V./V./Hr.; 5 min. on stream.]

Iron Oxide Content, Weight From these results it will be apparent relatively minor amounts of iron oxide when used in conjunction with titania greatly increase the conversion and/or selectivity. It is noteworthy that while carbon was produced when only 1% of iron oxide was used, no carbon was formed when 3% of iron oxide was used. With iron oxide as an addition agent the best results are obtained by using from 2 to 4% by weight of iron oxide. It is to be noted also that the better results ob tained when iron oxide was used were obtained at a considerably lower temperature than that employed when titania alone was used. It may be pointed out that in this particular example the iron oxide employed was a naturally occurring iron oxide known as specular hematite and that it was simply physically admixed with the titania.

EXAMPLE II Runssimilar to those reported in Example I were conducted with titania alone and with titania mixed with nickel oxide. In this case also the nickel oxide was merely physically admixed with the titania which was employed in the form of a naturally occurring oxide known as rut'ile ore. The operating conditions and the resultsare shown in the following table:

Methane oxidation with rutile ore plus NiOz [Fluid bed; 200 v./v./ hr.; atm. pressure] NiOg.Prcsent, Per Cent Zero 1 "3 'lcmperaturc F 1.690 1 7 5 Methane Conversion, Per Cent 9. 6 37. 8 1' 8 Selectivity To:

EXAMPLE III.

A set of runs similar to those'reported above were made using titania alone and titania with different amounts of chromium oxide. The results obtained are shown in the following table:

Methane oxidation with male ore plus can.

[Fluid bed; 200 v./v./hr.; atm. pressure] CnO; Present, Per Cent Zero 1 3 Temperature F 1.690 1, 710 l. 745 Methaue'Conversion, Per Cent 9. 6 49. 3 56.6 Selectivity To:

CO 2 2 l With this addition agent it will be observed that there was realized by the addition of chromium oxide a large increase in conversion without any decrease in selectivity. Actually with 3% by weight of chromium oxide the selectivity was almost 100%. It is noteworthy also that with this addition agent no carbon was formed. This'addition agent may be employed in amounts up to 25% by weight.

EXAMPLE IV Runs were made coresponding to those described in the previous examples using various amounts of an addition agent composed of 80 by weight of MO. The data obtained in these runs is compared in the following 'table with the data obtained when using titania alone:

Methane oxidation with rutile ore plus 80 FezOs-IO CI'203-10 NiO [Fluid bed; 200 v./v./hr.; atm. pressure] .80 Fe2O3-l0 017203-10 NioPresout, Percent Zero 2 4 6 10 Temperature "F 1.690 1. 720 l, 030 1, 68 0 1, 650 Methane Conversion Percent 9. 6 56. 7 64. 0 78. 5 93. 4 Selectivity To: 7 r

EXAIVIPLE V Runs similar to those described above were conducted when using varying amounts of a compound addition agent composed of 95% by weight of F6203 and 5% by weight of C1'2O3. The results obtained in these runs are compared in the following table with the results obtained when using titania alone. 7

Methane oxidation with rutile ore plus 95 Fe203-5 CrzOs [Fluid bed; 200 v./v./hr.; atm. pressure] 5 F6203-5 01'203 Pres- V ent, Percent Zero 2 5 10 15 25 Temperature F 1, 690 1, 700 1, 685, 1. 700 1, 640 1, 680

Methane Conversion,

Percent 9.6 56. 7 35. 5 77.3 8 2. 2 74.5 Selectivity To:

From the above data'it may be seen that while the addition agent effects a very large :increase in conversion with, in some cases, only a minor loss in selectivity as compared with the action of titania alone, the addition agent on the whole was not' as effective as that reported in Example IV.

'In all the foregoing examples the mixtures employed as oxygen carriers exhibited excellent fluidizing properties. These runs were all conducted in a quartz reactor.

Although in the foregoing description the specific operation described employed thefluidized solids technique, it is to be noted that in the practice of the present invention a fixed bed or a combination of a fixed bed and a fluidized solid bed may be employed. The pressure may be atmospheric or superatmospheric depending on design and economic considerations. -Pressures as high as 600 p. s. i. are contemplated. The feed rate ofthe hydrocarbon gas may vary widely depending on other operating conditions. In general permissible feed rates will be higher the higher the operating temperature and pressure. Feed rates as low as 100 volumes of gas per volume of oxygen carrier per hour are contemplated and this feed rate may be as high as 3000 v./v./hr. The residence time of the oxygen carrier in the hydrocarbon oxidation zone will vary and is a function of the circulating rates control between the reactor and the regenator required for temperature. This residence time is also a function of the oxygen. to metal ratio in the oxygen carrier at which high selectivities with CO production are obtained. This residence time may vary from about 5 to 30 minutes. In general it is preferred to have a residence time of the oxygen carrier in the hydrocarbon oxidation zone in the range of about 10 to 15 minutes.

The nature and objects of the present invention having been described and illustrated, what is claimed as new and useful and is desired to be secured by Letters Patent is:

1. A method for converting a gaseous hydrocarbon into a gas containing carbon monoxide and hydrogen which consists in contacting said hydrocarbon at a temperature of at least about 1600" F. with an oxygen carrier consisting essentially of a major proportion of titania in admixture with a minor proportion of an oxide of a metal commonly found in alloy steels andselected from the group consisting of iron, nickel, cobalt, manganese, chromium and tungsten.

2. A method according to claim 1 in which the oxygen carrier contains a major proportion of titania and minor proportions of oxides of at least two of the other metals enumerated.

3. A method according to claim 1 in which the oxygen carrier includes, in addition to titania, the oxides of iron, chromium and nickel.

'4. A method according to claim 1 in which the oxygen carrier contains more than about 90% by weight of titania.

5. In a method for converting a gaseous hydrocarbon into a gas containing carbon monoxide and hydrogen in which the gaseous hydrocarbon is passed upwardly through a contacting zone containing an oxygen carrier in the form of a finely divided solid at a velocity such as to maintain said finely divided solid in the form of a dense fluidized suspension while maintaining said contacting zone at a temperature of at least about 1600" F. and product gas is recovered from said contacting zone, the step which consists in employing as an oxygen carrier a finely divided solid consisting essentially of a mixture containing a major proportion of titania and a minor proportion of a metal commonly found in alloy steels and selected from the group consisting of iron, nickel, cobalt, manganese, chromium and tungsten.

6. A method according to claim 5 in which the oxygen carrier contains more than about 90% by weight of titania.

7. A method according to claim 5 in which the oxygen carrier contains a major proportion of titania and minor proportions of oxides of at least two of the other metals listed.

8. A method according to claim 5 in which the oxygen carriers contains, in addition to titania, the oxides of iron, nickel and chromium.

9. In a process for converting a gaseous hydrocarbon into a gas containing carbon monoxide and hydrogen in which there are maintained interconnected beds of finely divided solid oxygen carrier, gaseous hydrocarbon is passed upwardly through the first of said beds at a velocity sufficient to maintain said bed in a fluidized state at a temperature of at least about 1600 R, an oxidizing gas is passed upwardly through the second of said beds at a velocity sufficient to maintain said bed in a fluidized state at a temperature at which oxygen is added to said carrier, product gas is recovered from the first of said beds and finely divided solid continuously flows from each bed to the other, the step of employing as an oxygen carrier a mixture consisting essentially of titania and a minor proportion of an oxide of a metal commonly found in alloy steels and selected from the group consisting of iron, nickel, cobalt, manganese, chromium and tungsten.

10. A method according to claim 9 in which the oxygen carrier comprises a major proportion of titania and minor proportions of the oxides of at least two of the other metals listed.

11. A method according to claim 9 in which the oxygen carrier includes a major proportion of titania and a minor proportion of the oxides of iron, nickel and chromium.

EUGENE S. CORNER. ROBERT V. J. McGEE. CHARLES S. LYNCH.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 1,899,184 De Simo Feb. 28, 1933 2,042,285 Wilke et a1 May 26, 1936 2,425,754 Murphree et al. Aug. 19, 1947 2,507,502 Corner et al May 16, 1950 

1. A METHOD FOR CONVERTING A GASEOUS HYDROCARBON INTO A GAS CONTAINING CARBON MONOXIDE AND HYDROGEN WHICH CONSISTS IN CONTACTING SAID HYDROCARBON AT A TEMPERATURE OF AT LEAST ABOUT 1600* F. WITH AN OXYGEN CARRIER CONSISTING ESSENTIALLY OF A MAJOR PROPORTION OF TITANIA IN ADMIXTURE WITH A MINOR PROPORTION OF AN OXIDE OF A METAL COMMONLY FOUND IN ALLOY STEELS AND SELECTED FROM THE GROUP CONSISTING OF IRON, NICKEL, COBALT, MANGANESE, CHROMIUM AND TUNGSTEN. 